Acyclic terpene oxidation product and method of production



Patented Jan. 8, 1946 scromc manna oxms'rlon rnonuc'r Ann mn'rnon or raonUc'rloN Alfred L. Rnmmelsburg, Wilmington, Del., asslgnor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 31, 1941, Serial N0- 895,224

18 Claims. (CL 260-923) This invention relates new terpene oxidatlon products and to methods for their production: more particularly, it relates to oxidation products of acyclic terpenes having three double bonds per molecule and to methods for the production of the same.

y In accordanc withthi's invention, it has been found that an acyclic terpene, having three double bonds per molecule, will react with a free oxygen-containing gas, preferably in the presence oiwater, to produce a material which is waterinsoluble and a material which is water-soluble. The water-insoluble material can be separated further into a steam-volatile and a non-steamvolatile product. However, the water-soluble material contains substantially no steam-volatile constituents.

The non-steam-volatile,. water-insoluble product possesses theapproxlmate empirical formula (01081001) Vacuum distillation of this product gives a volatile oil having the approximate molecular formula CmHrsOz, and a resinous residue which is a mixture of various polymeric modiiications of the monomeric product. Some depolymerlzation to the monomer appears to take place in the distillation. Wherever, hereinafter, in this specification and claims, the water insoluble non-steam-volatile product 01' the oxidation of an acyclic terpene is referred to, the product resulting after the steam-volatile components have been removed from the waterinsoluble material is thereby contemplated.

The non-steam-volatile, water-solubl product prepared in accordance with this invention has been shown, on the basis of molecular weight and combustion analyses to consist mainly of a mixture of triand tetrahydroxy derivatives of the particular acyclic terpene employed. Thus, in the case ofallo-oci-mene the product will be a mixture of triand tetrahydroxy derivatives of allo-ocimene.

ized that any other acyclic terpenc having three double bonds per molecule may be equivalently employed. g

Allo-ocimene is an acylic terpene which, in addition to having a system of three double bonds, has them in a triply conjugated system. In its purified form it has the following average characteristics:

The terpene is a liquid characterized by a lightyellow color, an agreeable odor and a high refraction. It may be polymerized by various.

. methods, and the resulting products, particularly the dimeric modification, may be employed in practicing the present invention. However, it is preferred touse the monomer.

In carrying out the present invention, a1lo-' ocimene, or another acylic terpene, is contacted with oxygen, preferably in the presence of water. There are several methods of contacting these reactants. For example. the allo-ocimene and the water may be agitated and simultaneously blown with an oxygen-containing gas. Altera natively, the oxygen-containinggas may be par-- mechanically rocked. The oxygen-containing gas or such a gas containing vaporized R20 is In accordance with this invention; there may be employed as the starting material any acyclictially or completely saturated with water prior to contacting the-allo-ocimene. Another alternative, which is particularly applicable where superatmospheric pressure is being employed. i place the ailo-ocimene or allo-ocimene and ter. as desired. in a vessel which may be then introduced into the vessel and maintained as the case, may be, under the desired pressure with constant agitation.

'lireatment of allo-ocimene, or another terpene, with an oxygen-containing gas under 45 anhydrous conditions provides some reaction, but

the rate oi reaction is materially increased in the presence of water. The quantity of water which the proportion of water-soluble, men-stem volatile to water water-insoluble, non-steam- ,volatile products formed. In general. the lower the quantity of water used, the greater will be the percentage of water-insoluble, non-steamvolatile material formed; conversely, the greater. the quantity of water present, the lower will be the percentage of water-insoluble, non-steamvolatil mat'erial formed.

When water in liquid form is added directly to the allo-ocimene, or other acyclic terpene, during the reaction, it may be added in widely varying amounts. Preferably, however, an amount within the range of from about 1% to about 100% on the basis of the allo-ocimene is employed. When the water is introduced in the form of a vapor contained in the oxygen-containing gas,

' varying amounts may be employed, and the only tail! remains a water-insoluble, non-steam-volatile' product possessing the approximate empirical formula (CwHuOale. As a result 01' steam distillation of the oily, water-insoluble product, an

aqueous phase usually forms. This phase usually contains small amounts of extracted water-soluble product. 'Hence, this aqueous phase can be limitation is the point of saturation of the oxygen-containing gas. If desired, additional water in liquid form may be added to the allo-ocimene or other acyclic terpene.

The temperature of contacting is not critical and may desirablv be within the ran e from about 0 C. to about 150' C. A temperature from about '20 C. to about 50' C. is preferred. The'reaction itself is exothermic. the heat evolved being de- Y pendent upon the rapidity with which the reaction is allowedto progress. The time of reaction is dependent upon other conditions such as pressure, temperature. etc.. employed. the quantity of oxygen immediately contacting the allo-oclmene. and may vary within the range of from about 2- hours to about 2 weeks. Under preferred conditions, a reaction time of from about 8 hours to about 150 hours is suillcient. The oxygen-containing as may be used at reduced. normal or at superatmospherlc pressure. Contacting at superatmospheric pressure. and in particular. at a pressure within the range of from about 100 to 2000.

. lbs. per sq. in.'. is preferred where rapid reafetion and a high yield of water-insoluble. non-steamvolatile product is desired.

The reaction-may be accelerated. ii desired, by means of a catalyst. Suitable catalysts are oxi- 1 dation catalysts, and of these the preferred cata-"' lists-are the naphthenates, stearatesand resinates of cobalt, man anese and lead. Other'materlals which exhibit catalytic action comprise activated carbon, flake aluminum. iron ppwder. lead mercaptides, ammonium chloride. selenium dioxide, vanadium pentoxide. ammonium vana-.

' date. etc. The use of a catalyst generally tends to reduce the-amount of water-soluble. non steam-volatile product. When used, the catalyst will be used'preferably' in an amount up to about 10% based on thmweight of the allo-ocimene.

' Larger amounts may be used. if desired.

The oxygen-containing gas employed in the reaction is one which contains free oxygen with or without other gases which are inert to the reactantsor the products. Thus. free oxygen. air, etc.. may be employed.

Depending upon the particular procedure employed to accomplish reaction, the reaction product will be found to consist of one or two phases. There will usually be two phases resulting when water in liquid form is added to the acyclic ter-' pene prior to or during reaction. One of these phases will be an aqueous phase and the other an oily. water-insoluble phase. In accordance with this invention, the oily phase will be separated and steam distilled to remove an steam-volatile terpenes, also any steam-volatile oxygenated terpcnea. If desired, the entire reaction mixture ture prior to steam distillation. Evaporation of the water by distillation at atmospheric pressure or in vacuo leaves the water-soluble product as the residue.

Alternatively, .when the reaction mixture is homogeneous, as for example when no water is employed in the processor when small amounts of water vapor are presentin the oxygen-containing gasemployed in contacting the acyclic terpene, the entire reaction ure ay be extracted with water to remove the r-soluble product. The water-insoluble portion may be separated and treated as hereinbefore described, i. e., steam distilled to yield a product which is water-insoluble and non-steam-volatile; "If desired, the homogeneous reaction mixture may be steam distilled prior to extraction with water.

Either a pure or impure form of allo-oclmene or other acyclic terpene may be employed in carrying out the processes of the invention, although a relativel v pure starting material is preferred. Thus, mixturesof allo-ocimene with other less reactive terpenes such as a-pinene. B-pinene, terpinene, dip'entene, etc., may be used. The product resulting from the pyrolysis of a-pinene. for example, may be used. When vaporized apinene. is heated at elevated temperatures. an isomerization takes place which results in a product which may contain as much as 40% alloocimene or more, depending upon the particular conditions employed. In addition to the alloocimene, there will bepresent e-pinene. dipentene and other complex hydrocarbons. This crude' allo,-ocimene mixture may be concentrated by distillation. Where impure allo-ocirnene is 'employed, the allo-ocimene content preferably should be at least about 40% by weight.

There follow several examples which illustrate specific embodiments of thisinvention. These ex.

amples, however, are not to, be taken as beinglimiting. All percentages are by weight unless otherwise indicated.

. Exams: 1

Eight hundred and sixteen grams of 96% alloocimene was blown with moist air at a tempera-- The latter was separated from the former which was evaporated to remove the water present. The

product was a water-soluble resin. The'blowing operation :was continued and additional samples. taken at intervals.- These samples gave analyses as indicated in the following table. The figures in the "Time" column show the, total interval 'fms be steam distilled. However, it is simpl we ow elapsed from the inception of the blowing operaaaaaers v 3 I As illustrative oi the .methods oi obtaining the phase and an aqueous phase. The aqueous phase approximate formulas of the products oi the was separated and vacuum -distilled 'to yield a invention, 20 grams of the water-insoluble. nonwater-soluble resinous product. Thus, the resteam-volatile resin obtained as a result or the 1 action product was ioundtoconsistot:

99-hour run were vacuum distilled at 3 to 6 mm. pressure. Two grams oi distillate passed over at Ste 1 d] Per a; a vapor temperature 155 0. Analyses of the z e original sample and the distillate as compared mn'mam'voume 45 with theoretical I mouow: 2 Water-insoluble. non-steam volatile 28 In the ioliowinl examples a crude form of allopm M01 ocimene was employed. This crude allo-ocimene g me an was one obtained from the pyrolysis or-a-pinene. 7 0H 0 H (mm It consisted of 40% allo-ocimene in conjunction 25 with s-pinene, dipent'ene.', and a relatively small 405 quantity 0! complex unidentified hydrocarbons.

714 as 2%; 3;; g: In certain of the examples to follow this crude g; s allo-ocimene was concentrated to 65% allois: ocimene by distillation. I f i Exam? It is apparent that the distillate compares tavorbl withacomun h on s g 616K160; g gg g zg 85' C. while passing a current or air through the original watebmso'mblei n'omsteamwolame w 8| mixture at a rate of to liters per hour for not was a polymeric modification oi the distillate perm! The "actkm mixture was and that decomposition in the form or damn steam distilled'to remove the steam-volatile con- Water Thirty-seven grams of water-soluble nonheated to m t water steam-volatile resin from-the 99-hour run were soluble which were isolated by vacuum distillation of the extract. In this man- {mixture oi 600 grams of allo-ocim'ene (40%. pure) andfltoo grams of'water was agitated at Y vacuum distilled at 4 m u l me 1on0": ner-,-the reaction product was found to consist of:

w Pea r Mom Percent moa' amt Steam-volatile .71

- 0 a (Best) 48 llVater-solublc,v non-stearn-volatile 10 1: g: to: Water-insoluble, nonsteam-volatile 19 is :01 last Zm m! w 5 Fifty grams or allo-ochnene (40% pure) were placed in a rocking-type stainless steel pressure M I bomlinigovngea czpggitg) (5:0 500 cc. iOxygen gas rms Per s was u a C. untl a pressure H $33 of to lbs. per sq. in. developed. Agitation was commenced. After about 2 hours. the pressure 187 had dropped to 30 lbs. per sq. in., at which point it was incr eased'to lbs; per sq. in. by adding w more oxygen. Thereafter, whenever the oxygen m pressure dropped to lbs. per sq. in. it was increased to a pressure between 60 and 200 lbs.

On the basis of the above data, the waterper sq. in. by adding morev oxy'g'en.*After a soluble resin obtained in accordance with this total reaction period-oi 54 hours; about 0.4 gram invention is a poly-oxygenated alio-ocimene and moi-of oxygen had been absorbed, based on the coooo probably consists mainly of trihydroxy and tetrapressure changes. The. reaction mixture had inhydroxy derivatives 0! allo-oeimene. creased in weight about 14 grams. Employing m 2 j the same processes as in Example 3, the reaction mixture was found to consist of: A mixture oi 357 grams of allo-ocimene Per cent and 350 grams of water was blown with oxyl i 8team volaflle 52 while the mixture was beins s ted. The blow- Water-soluble, non-steam-volatile 15 in: operation was continued for 33 hours at a Water-insoluble, non-steam-volatile 33 temperature of 25 to 35' C. using an omen v m5 w velocity of 20 to 25 liters per hour. The reaction 7 mixture was steam distilled to remove steam-- riiteenhrmdredgrsmsoracrudealln -ocimene volatile constituents. The residue was-round to containinrm were blown with consist oi two phases. an oil! water-insoluble "moistairatiitodb' c.toraperiod-ct35hours with agitation. The air velocity was held constant at 5-10 bubbles per second. Analysis showed the product'to have the iollowlng characteristics:

P 12,5 (3, "f -9 Acid number 2. 8 Saponification number 28. 0

Two hundred and thirty-two grams of this matelo rial were steam distilled as in the previous examples to yield four diii'erent products. A being the steam-volatile unreacted terpenes, B being the steam-volatile terpenes containing volatile ketones, C being the non-steam-volatile, waterinsoluble material and D being the non-steam volatile, water-soluble material. The results follow: v

Yield, grams Exams: 6

4 A 3150-gram quantity of 40% alio-ocimene was blown with moist air at a velocity of to liters per hour and at a temeprature of 25 during 'the blowing operation representative samples were taken and steam distilled to separate the steam-volatile components. The residue was extracted with water heated to about C.-to remove the water-soluble constituents. The water-soluble constituents were then isoto 30 C. with agitation. At various intervals 'asaaeis reaction mixture obtained in accordance with this invention, the reaction mixture itself may be employed and possesses great utility in the textile and ore flotation fields.

It will be understood that the details and examples hereinbeiore set forth are illustrative only and that the invention as broadly described and claimed is in no way limited thereby.

What I claim and desire to protect by Letters Patent is: v

l. A method for the production of an oxygenated acyclic terpene which comprises reacting an acyclic terpene having three double bonds per molecule with water and. a gas containing tree oxygen. as the sole reactive gas, at a temperature of from about 0 C. to about C. until an appreciable portion 01 the acyclic terpene' has reacted with the water and tree oxygen to form .a mixture of water-soluble and water-insoluble oxygenated acyclic terpenes.

2. A method. for the production of an oxygenated acyclic terpene which comprises reacting allo-ocimene with water and a gas containing tree oxygen, as the sole reactive gas. at a temperature of from about 0' C. to about 150 C.

until an appreciable portion of the allo-ocimenehas reacted with the water and free oxygen to form a mixture of water-soluble and water-insoluble oxygenated acyclic terpenes.

3. A method for the production of an oxygenated acyclic terpene which comprises reacting myrcene with water and a gas containing free oxygen, as the sole reactive gas. at a temperature of from about 0' C. to about 150C. until an appreciable portion of the myrcene has reacted with the water and free oxygen to form. a mixture of water-soluble and water-insoluble oxygenated lated by vacuum distillation. The results follow: acycllc'terpenes.

Table 2 I P m t Pergmt Par fit Time, a 15.6'0. Sample, 1 '5, n, m 8p. gr. m um "um. son 1m 15.0]! n non volatile volatile 0.8666 sec I cam am as a 1m asm es: com me see me m4 cm: was 0.9!!! 181.6 mm was V cm ass no m as Exam-u 7 4. A method for the production of an oxy- Five hundred grams of 65% allo-oclmene and u 500 grams 0! water were air blown with agitation for 26 hours at a temperature oi 25 to 32 C. The air velocity was held at approximately 40 liters per hour. The resulting product was steam distilled and the constituents separated in the o manner oi the previous example. The results iollow: 4 1

Per cent Steam-volatile T a 36.4 Water-soluble. non-stesm-volatile 48.5 as Water-insoluble, non-steam-volatile. ital The water-soluble, non-steam-volatile prod,- ucts 01- this invention may be used as softening oi ores. The water-insoluble resins are useful in the formulation of paints. lacquers and varniches, also in the notation of ores.

In addition to the products separable trom the genated acyclic terpene which comprises reacting allo-ocimene with water and air, at a tempera ture oi irom about 0' C. to about .150 C. until an appreciable portion oi. the allo-ocimene has reacted with the water and tree oxygen to form a mixture 01 water-soluble and water-insoluble oxygenated acyclic terp'enes.

5. A method for the production of an oxy- I genated acyclic icrpene which comprises reacting myrcene with water and air at a temperature cl 1 genated acyclic terpene which comprises reacting alio-ocimene with water and air in the presence 0! an oxidation catalyst at a tcmperatureoi'ironi about 0' C. to about 150' 0. until an appreciable portion 0! the allo-ocimene has reactedv with the waterandlreeoaygentoiormamixtureoiwatersoluble and water-inaoluble oxygenated acyclic terpenes.

'l. A method for the production of an oxygenated acyclic terpene which comprises reacting myrcene with water and air in the presence or an oxidation catalyst at a temperature of from about C. to about 150' C. until an appreciable portion oi! the myrcene has reacted with the water and tree oxygen to form a mixture of water-soluble and water-insoluble oxygenated acyclic telpenes.

8. A method for the production of an oxygenated acyclic terpene which comprises reacting allo-ocimene with water and air in the presence of an oxidation catalyst at a temperature of from about 20' C. to about 50! C. until an appreciable portion of the allo-ocimene has reacted with the water and tree oxygen to form a mixture of waacyter-soiuble and water-insoluble oxygenated clic terpenes. a. A method for the production oi an oxygenated acyclic terpene which comprises reacting myrcene with water'and 'air in the presence of an oxidation catalyst at a temperature of from about 20' C. to about 50' C. until an appreciable portion of the myrcene has reacted with the water and tree oxygen to form a mixture or water-solubio and water-insoluble oxygenated acyclic terpenes.

10. As a new composition of matter, an oxy-- genated acyclic terpene formed by reacting an acyclic terpene having three double bonds per' gen, as the sole reactive gas, at a temperature of' from about 0' C. to about 150 C. until an appreciable portion of the allo-ocimene has reacted with thewater and tree oxygen. .12. As a new composition of matter, an oxygenated acyclic terpene formed by reacting myrcene with water and a gas containing i'ree oxygen.

aaeae'ia aetheaolereactivegaaatatemperat u-eoflrom i aboutirc. toaboatlso'auntilanappreeiabh portionoithemyrcenehaareactedwiththewatar and tree oxygen.

13. A water-soluble, nonsteam-volatile oxygenated acyclic terpene formed by reacting alloocimene with water and a gas containing tree oxygen. as the sole reactive gas. at a temperature of from about 0'- C. to about C. until an appreciable portion of the allo-ocimenehas re acted with the water and tree oxygen to term a mixture of water-soluble and water-insoluble oxygenated acyclic terpenes, and recovering the water-soluble, nonsteam-volatile product.

14. A water-insoluble, ncnateam-volatile 0X!- genated acyclic terpene having the empirical formula (0:03am): in which a: is a whole number greater than one. said product being formed by reacting allo-ocimen with water and a gag com taining tree oxygen, as the sole reactive gas. at a temperature of from about 0' C. to about 1W 0. until an appreciable portion of the alio-ocimene has reacted with the water and tree oxygen to form a mixture of water-soluble and vwater-insoluble oxygenated acyclic terpenes, and recovering the water-insoluble, nonsteam-volatile product.

. 15. A water-soluble, oxygenated acyclic terpene containing at least three hydroxyl groups, said product being formed by reacting allo-oclmene with water and a gas containing iree oxygen. as the sole reactive gas, at a temperatureo! from about 0 C. to about 150' C. until an appreciable portion of the allo-ocimene has reacted with the P uct.

AII'RED a. a. 

